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C. R. Reddy et al. / Tetrahedron 61 (2005) 1289–1295
1.66–1.62 (m, 4H), 1.42–1.39 (m, 4H), K0.05 (s, 9H); 13
C
166.7, 139.8, 134.0, 132.8, 130.5, 129.6 (2C), 128.5, 128.3,
128.0 (2C), 127.8 (2C), 72.9, 70.2, 65.0, 29.7, 28.7, 26.8,
26.0 (2C), K1.9 (3C); IR (neat): 711, 854, 1107, 1275,
1720, 2856, 2946 cmK1; HRMS (ESI): calcd for
C24H34O3Si, 421.2175 (MCNa)C, found 421.2184.
NMR (CDCl3): d 140.0, 138.9, 134.8, 128.6 (2C), 128.3,
128.2, 128.0 (2C), 127.9 (2C), 127.7, 73.1 (2C), 70.6, 70.5,
30.0 (2C), 27.0, 26.3 (2C), K1.7 (3C); IR (neat): 847, 1099,
1242, 2853, 2931 cmK1; HRMS (ESI): calcd for
C24H36O2Si, 407.2382 (MCNa)C, found 407.2371.
4.2.16. tert-Butyl(dimethyl){[6-({4-[(trimethylsilyl)-
methyl]benzyl}oxy)hexyl]oxy}silane (5o). Colorless oil;
1H NMR (CDCl3): d 7.17 (d, 2H, JZ7.6 Hz), 6.96 (d, 2H,
JZ7.6 Hz), 4.43 (s, 2H), 3.60 (t, 2H, JZ6.4 Hz), 3.45 (t,
2H, JZ6.4 Hz), 2.07 (s, 2H), 1.3–1.58 (m, 2H), 1.55–1.50
(m, 2H), 1.40–1.31 (m, 4H), 0.89 (s, 9H), 0.04 (s, 6H),
K0.02 (s, 9H); 13C NMR (CDCl3): d 140.0, 134.3, 128.2
(2C), 128.0 (2C), 73.1, 70.5, 63.4, 33.1, 30.0, 27.0, 26.2
(3C), 25.9, 25.8, 18.6, K1.7 (3C), K5.0 (2C); IR (neat):
776, 858, 1099, 1250, 2856, 2933 cmK1; HRMS (ESI):
calcd for C23H44O2Si2, 447.2517 (MCNa)C, found
447.2513.
4.2.11. Trimethyl{4-[({6-[(4-methylbenzyl)oxy]hexyl}-
oxy)methyl]benzyl}silane (5j). Colorless oil; 1H NMR
(CDCl3): d 7.23 (d, 2H, JZ7.6 Hz), 7.18 (d, 2H, JZ7.6 Hz),
7.15 (d, 2H, JZ7.6 Hz), 6.97 (d, 2H, JZ7.6 Hz), 4.46 (s,
2H), 4.44 (s, 2H), 3.45 (dd, 4H, JZ6.4 Hz), 2.34 (s, 3H),
2.07 (s, 2H), 1.60 (m, 4H), 1.38 (m, 4H), K0.02 (s, 9H); 13C
NMR (CDCl3): d 139.8, 137.1, 135.7, 134.1, 129.0 (2C),
128.0 (2C), 127.8 (2C), 127.8 (2C), 72.9, 72.8, 70.3, 70.2,
29.7, 27.1, 26.8, 26.1 (2C), 21.2, K1.8 (3C); IR (neat): 694,
857, 1098, 1245, 1507, 2949 cmK1; HRMS (ESI): calcd for
C25H38O2Si, 437.2278 (MCK)C, found 437.2263.
4.2.12.
{4-[({6-[(4-Methoxybenzyl)oxy]hexyl}oxy)-
4.2.17. tert-Butyl(diphenyl){[6-({4-[(trimethylsilyl)-
methyl]benzyl}oxy)hexyl]oxy}silane (5p). Colorless oil;
1H NMR (CDCl3): d 7.70 (m, 4H), 7.41 (m, 6H), 7.21 (d,
2H, JZ7.6 Hz), 6.99 (d, 2H, JZ8.4 Hz), 4.46 (s, 2H), 3.68
(t, 2H, JZ6.4 Hz), 3.47 (t, 2H, JZ6.4 Hz), 2.09 (s, 2H),
1.67–1.57 (m, 4H), 1.44–1.30 (m, 4H), 1.07 (s, 9H), 0.01 (s,
9H); 13C NMR (CDCl3): d 140.0, 135.8 (4C), 134.5 (4C),
134.4 (2C), 129.8 (2C), 128.3 (2C), 128.0, 127.9 (2C), 73.2,
70.6, 64.2, 32.8, 30.1, 27.2 (3C), 27.1, 26.3, 26.0, 19.5.
K1.6 (3C).; IR (neat): 702, 845, 1107, 1246, 1511, 2852,
2933 cmK1; HRMS (ESI): calcd for C33H48O2Si2, 571.2830
(MCK)C, found 571.2850.
methyl]benzyl}(trimethyl)silane (5k). Colorless oil; 1H
NMR (CDCl3): d 7.29 (d, 2H, JZ8.4 Hz), 7.21 (d, 2H, JZ
7.6 Hz), 6.99 (d, 2H, JZ7.6 Hz), 6.90 (d, 2H, JZ8.4 Hz),
4.46 (s, 4H), 3.83 (s, 3H), 3.46 (dd, 4H, JZ6.4, 13.2 Hz),
2.09 (s, 2H), 1.68–1.60 (m, 4H), 1.42–135 (m, 4H), 0.01 (s,
9H); 13C NMR (CDCl3): d 159.1, 139.8, 134.0, 130.8, 129.2
(2C), 127.9 (2C), 127.7 (2C), 113.7 (2C), 72.8, 72.5, 70.3,
70.1, 55.3, 29.7 (2C), 26.8, 26.1 (2C), K1.9 (3C); IR (neat):
845, 1099, 1246, 1511, 2856, 2933 cmK1; HRMS (ESI):
calcd for C25H38O3Si, 437.2488 (MCNa)C, found
437.2470.
4.2.13. 2,2-Dimethyl-15-{4-[(trimethylsilyl)methyl]-
phenyl}-5,7,14-trioxa-2-silapentadecane (5l). Colorless
oil; H NMR (CDCl3): d 7.17 (d, JZ7.6 Hz, 2H), 6.95 (d,
4.2.18. Trimethyl[4-(2,9,11,14-tetraoxapentadec-1-yl)-
benzyl]silane (5q). Colorless oil; 1H NMR (CDCl3): d
7.17 (d, 2H, JZ7.6 Hz), 6.96 (d, 2H, JZ7.6 Hz), 4.70 (s,
2H), 4.42 (s, 2H), 3.68 (t, 2H, JZ6.4 Hz), 3.56–3.51 (m,
4H), 3.45 (t, 2H, JZ6.4 Hz), 2.06 (s, 2H), 1.61–1.57 (m,
4H), 1.41–1.34 (m, 4H), K0.02 (s, 9H). 13C NMR (CDCl3):
d 139.8, 134.0, 128.0 (2C), 127.7 (2C), 95.5, 72.9, 71.8,
70.3, 67.9, 66.7, 59.0, 29.7, 29.6, 26.8, 26.1, 26.0, K1.9
1
JZ7.6 Hz, 2H), 4.65 (s, 2H), 4.42 (s, 2H), 3.60 (t, JZ8.4,
16.8 Hz, 2H), 3.52 (t, JZ6.8, 13.2 Hz, 2H), 3.45 (t, JZ6.8,
13.2 Hz, 2H), 2.06 (s, 2H), 1.61–1.56 (m, 4H), 1.38–1.25
(m, 4H), 0.93 (t, JZ8.4, 16.8 Hz, 2H), 0.01 (s, 9H), K0.02
(s, 9H); 13C NMR (CDCl3): d 140.0, 134.2, 128.2 (2C),
128.0 (2C), 95.0, 73.1, 70.5, 68.0, 65.1, 29.9 (2C), 27.0,
26.3, 26.2, 18.3, K1.2 (3C), K1.7 (3C); IR (neat): 854,
1061, 1106, 12.52, 2863, 2945 cmK1; HRMS (ESI): calcd
for C23H44O3Si2, 447.2727 (MCNa)C, found 447.2726.
(3C); IR (neat): 853, 1045, 1106, 1249, 1511, 2933 cmK1
;
HRMS (ESI): calcd for C21H38O4Si, 421.2176 (MCK)C,
found 421.2159.
4.3. General procedure for the deprotection of TIX
ethers
4.2.14. 6-({4-[(Trimethylsilyl)methyl]benzyl}oxy)hexyl
acetate (5m). Colorless oil; H NMR (CDCl3): d 7.20 (d,
1
2H, JZ7.6 Hz), 6.99 (d, 2H, JZ7.6 Hz), 4.46 (s, 2H), 4.07
(t, 2H, JZ6.4 Hz), 3.48 (t, 2H, JZ6.4 Hz), 2.09 (s, 2H),
2.06 (s, 3H), 1.70–1.62 (m, 4H), 1.46–1.36 (m, 4H), 0.00 (s,
9H); 13C NMR (CDCl3): d 171.2, 139.8, 134.0, 128.0 (2C),
127.7 (2C); 72.9, 70.1, 64.5, 29.6, 28.6, 26.8, 25.9, 25.8,
21.0, K1.9 (3C); IR (neat): 854, 1103, 1246, 1740, 2860,
2950 cmK1; HRMS (ESI): calcd for C19H32O3Si, 359.2018
(MCNa)C, found 359.2027.
The TIX ether (1 mol equiv) was taken in dichloromethane:
water (9:1 or 5 mL/mmol). To this well stirred solution was
added DDQ (1 mol equiv) at room temperature (generally
15–60 min). After completion of the reaction (as monitored
by TLC for disappearance of starting material), the reaction
mixture was filtered, and the filtrate was washed with
dichloromethane (10 mL). The combined organic layers
were washed with a saturated aqueous solution of NaHCO3,
brine, dried (anhydrous Na2SO4), filtered and concentrated.
Purification of the residue was readily achieved by flash
column chromatography (silica gel 60, EtOAc/hexanes)
affording the alcohols in excellent yields (Table 3).
4.2.15. 6-({4-[(Trimethylsilyl)methyl]benzyl}oxy)hexyl
benzoate (5n). Colorless oil; H NMR (CDCl3): d 8.07 (d,
1
2H, JZ7.2 Hz), 7.58 (t, 1H, JZ7.6 Hz), 7.46 (t, 2H, JZ
7.2 Hz), 7.20 (d, 2H, JZ7.6 Hz), 6.99 (d, 2H, JZ7.6 Hz),
4.47 (s, 2H), 4.34 (t, 2H, JZ6.4 Hz), 3.50 (t, 2H, JZ
6.4 Hz), 2.09 (s, 2H), 1.83–1.76 (m, 2H), 1.70–1.62 (m, 2H),
1.54–1.42 (m, 4H), 0.01 (s, 9H); 13C NMR (CDCl3): d
4.3.1. 1-Methyl-4-[(3-phenylpropoxy)methyl]benzene
1
(4a0). Colorless oil; H NMR (CDCl3): d 7.36–7.22 (m,
9H), 4.54 (s, 2H), 3.54 (t, 2H, JZ6.4 Hz), 2.78 (t, 2H, JZ